The geometries and electronic spectra of a series of N-protonated corroles, including unsub- stituted H4Cor＋ and meso-triaryl substituted H4TPC＋, H4TpFPC＋, and H4TdCPC＋, were theoretically studied with density fun...The geometries and electronic spectra of a series of N-protonated corroles, including unsub- stituted H4Cor＋ and meso-triaryl substituted H4TPC＋, H4TpFPC＋, and H4TdCPC＋, were theoretically studied with density functional theory （DFT）. The results indicate that all these compounds have two conformers, one with C2 symmetry （denoted as Sl） is more stable than the other （denoted as $2, C1 symmetry） by 15.8-18.5 kJ/mol. The corrole macrocycles of these compounds show significant out-of-plane deformation. The enantiomerizations of the chiral S1 conformers were found to be a multi-step process with the $2 conformers as the intermediates. Electronic absorption spectra and electronic circular dichroism （ECD） of these compounds were calculated with time-dependent DFT. In comparison with H4Cor＋, the UV- Vis absorptions of meso-triaryl species are significantly red-shifted and their Q bands are enhanced due to the π-π conjugation between the aryl and corrole rings. Several neighboring electronic transitions were calculated with opposite signs in rotatory strengths, suggesting that ECD spectroscopy may be a useful tool in studying the electronic transitions of these compounds.展开更多
文摘The geometries and electronic spectra of a series of N-protonated corroles, including unsub- stituted H4Cor＋ and meso-triaryl substituted H4TPC＋, H4TpFPC＋, and H4TdCPC＋, were theoretically studied with density functional theory （DFT）. The results indicate that all these compounds have two conformers, one with C2 symmetry （denoted as Sl） is more stable than the other （denoted as $2, C1 symmetry） by 15.8-18.5 kJ/mol. The corrole macrocycles of these compounds show significant out-of-plane deformation. The enantiomerizations of the chiral S1 conformers were found to be a multi-step process with the $2 conformers as the intermediates. Electronic absorption spectra and electronic circular dichroism （ECD） of these compounds were calculated with time-dependent DFT. In comparison with H4Cor＋, the UV- Vis absorptions of meso-triaryl species are significantly red-shifted and their Q bands are enhanced due to the π-π conjugation between the aryl and corrole rings. Several neighboring electronic transitions were calculated with opposite signs in rotatory strengths, suggesting that ECD spectroscopy may be a useful tool in studying the electronic transitions of these compounds.
